Photographic elements containing mordants



Patented Apr. 13, 1954 PHOTOGRAPHIC ELEMENTS CONTAINING MORDANTS Burt H. Carroll and Willi-ant d. Kenyon, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application April 14, 1949, Serial No. 87,578

1i Claims.

i This invention relates to improvements in photographic layers and more particularly to inn- {movements in mordant compositions adapted to fix soluble dyes therein.

Many photographic color processes involve the use of a soluble acid dye in a photographic layer. The dye may serve. as a light filter or may be used as a light-absorbing backing for the film to prevent reflection of light back into the emulsion. Soluble dyes of this type are commonly used in relief imbibition printing where the dye is transferred from a tanned gelatin relief to a gelatin coated paper. In eachof these processes, it is essential. that the dye; be fixed against diffusion to prevent its bleeding. out of the: areato which it was originally confined. In order to accomplish fixing agents or mordants. have been used.

We have found that the efiectlveness of basic mordant compositions in preventing dye diffusion is dependent upon three factors. The. first factor is degree of ionization. Since simple salt formation is believed to be the basis of this type of mordant action, the mordant must be well ionized at the particular pH existing at the point of fixation. high degree of ionization will lessen the quantity of mordant required to a given amount of dye' Secondly, the mordant must possess sufficiently large molecular dimensions so that the mordant-dye salt formed will not diffuse through the colloid. The third factor is one of solubility. The mordant must be waterdispersible and compatible with the gelatin, or other colloid used.

According to our invention, these requirements for an improved mordant composition may he fulfilledby the use of an addition type polymer containing periodically occurring amino groups, such as tertiary amino groups.

mordants which presumably form a molecular combination with chelat'e groups in the dye. The

polymericstructure of: our compounds provides a high molecular weight while the presence of periodically-occurring, amino groups results in a: moderate equivalentv weight. The amino groups may be quaternized to increase ionization and solubility. Included in our invention are all homopolym-ers, copolymers, or derived. polymers having an alkyl amine substituent of the structure stated above and the quaternized form of such substances. Where we refer to polymers it is to be understood that all such. substances are included.

The quaternary compounds are water-soluble, but some of the unquaternized polymers are not water-soluble, and must be introduced to the gelatin in the form of theirsalts, e. g., the acetate, which are water-soluble. Where the claims refer to the; unquaternized compounds, it is to be understoodthat this includes their simple salts, where the compounds themselves are not water-soluble.

Examples of compounds useful for the purposes of our invention are as follows:

1. Esters or amides prepared by reacting addinon polymers containing carboxyl groups witha basic dialkylamino compound.

(a) N-dialkyl amine ethyl esters of polymers or copolymerscontaining carboxyl groups. These polymeric substances may be produced by reacting resins having combined acrylic, methmay be employed. The preparation of themonomeric esters is described in Graves U. S. Patent Th e polym rs are alkyl amine o the fol- 2,138,763, granted November 29, 1938. lowing structure:

Example 1.Prepamtwn of poZydze-thylammo ethyl methacrylate Eighty grams of the monomeric p-diethylamino ethyl methacrylate were settled into a Pyrex glass tube and irradiated for eight days at a distance of 12 inches by light from a 250-volt Cooper- Hewitt mercury quartz are, operating at 1 am- .peres. A very light yellow, viscous, clear dope. was

obtained. This was poured.v into 3 liters of 1:1

methanol and water to precipitate the polymer, which" was then" extracted with use portions of 1:1 methanol and water. It was dried in a Majonmer oven at 5Q? (3.. under a vacuum of 28 inches 01 mercury. new was 26 rams.

3 For quaternization, see Example 12 of Minsk and Kenyon patent application Serial N 0. 719,626, filed December 31, 1946 now U. S. Patent 2,484,420, granted October 11, 1949.

Example 2 A reaction product of p-dimethylaminoethyl alcohol and polymethacrylic anhydride was prepared as follows:

One hundred grams of methacrylic anhydride, 300 mgs. benzoyl peroxide, and 400 cc. dry dioxane were heated under steam bath reflux. After 15 minutes, the polymethacrylic anhydride had set to a white solid mass. After two hours, 200 grams of redistilled s-diethylaminoethyl alcohol were added and the heating continued for 16 hours. The resulting dope was precipitated in rapidly stirred acetone. It was washed in fresh acetone and then dried. A yield of 115 grams was obtained.

A'quaternary salt was prepared by heating 2.71 grams of the p-diethylaminoethyl polymethacrylate ester on the steam bath for 6 /2 hours with 2.52 grams of methyl sulfate. The mixture bubbled up to several times its volume and remained sticky and glossy. It was cooled and stirred with several fresh portions of acetone to remove excess methyl sulfate, then air dried.

(12) Polymers or copolymers prepared as in (a) by reacting the resin with an amine of the type: v

\N- (Grim-o Hz-NH: R

wherein R iS CH3, CH3(CH2)1I 11:1, 2,3

Example 3.Preparation of polyacrylyl amide of 5-diethylamz'no-2-amino pentane Forty grams of 5-diethylamino-2-amino pentane were dissolved in 200 cc. of dry acetone in a glass outfit equipped with a stirrer, a dropping funnel and a reflux condenser protected by a calcium chloride tube. The reaction mixture was chilled in an ice bath. To this was added dropwise, with stirring, 200 grams of a per cent solution by weight of polyacrylyl chloride in dry acetone. The product precipitated as a mass during the addition of the acid chloride. After all the acid chloride had been added, the reaction mixture was stirred for 1.5 hours at room temperature, and then for one hour at reflux. The acetone was then decanted and the solid product extracted repeatedly with fresh portions of acetone with mechanical stirring. The product was dried in a vacuum desiccator under constant water pump: vacuum. The yield was 39 grams. Nitrogen and chlorine were 10.2 and 12.8 per cent respectively. The calculated values were 11.2 and 14.2.

Quatemization.--Ten grams of the above polymer were dispersed on as'haker in 100 cc. of methyl Cellosolve. To this was added cc. of a 4 per cent solution by weight of sodium in ethyl alcohol. The dope was filtered to remove the precipitated sodium chloride, Fifteen cc. of methyl p-toluene sulfonate was then added and the reaction mixture heated on a steam bath in an all-glass reflux outfit protected by calcium chloride for 18 hours. The clear, smooth dope stirring. The product precipitated as a light yellow, friable precipitate which was then extracted thoroughly with fresh portions of ether. It was dried in a vacuum desiccator under constant water pump vacuum. The yield was 14.5

obtained was then filtered through paper by suc-' 1 tion and poured into 1.5 liters of ethyl ether with 2. Polymers or copolymers of compounds having a combined N-vinyl dialkylamine group and containing the basic unit CHn-?H where R1 and R2 are CH3, CH3(CH2)1L or alicyclic groups, e. g., cyclohexyl, or together represent the atoms necessary to complete a saturated heterocyclic ring, e. g., piperidine or morpholine, andn=1,2,3.

Example 4 A reaction product of diethylamine and a vinyl benzene sulfonate-vinyl alcohol copolymer was prepared as follows:

Forty grams of polyvinyl benzene sulfonate was mixed with 300 cc. of anhydrous dicxane, 20 cc. of water, and grams of anhydrous diethyl- 1 amine in a sealed flask. The flask was shaken to effect solution and was placed in a bath at 60 C. for 7 days. The resulting viscous solution was filtered, concentrated to a suitable volume and precipitated in water. The resulting resin was leached and dried, and found to be insoluble in water but soluble in dilute acid. Its structure is believed to be as follows:

A reaction product of piperidine and a vinyl benzene sulfonate-vinyl alcohol copolymer was prepared as follows:

Thirty grams of polyvinyl benzene sulfonate was dried thoroughly over P205 in vacuum at room temperature. Anhydrous piperidine cc.) was added to this resin in a flask, the flask evacuated, and nitrogen added. The reaction mixture was kept at 50 C. for six days, after which the product was filtered and precipitated in water. A yellow resinous product was separated and leached with water. It was dried, dissolved in ether, filtered, poured into water, leached and dried. It is believed to contain the following basic unit:

. CH2-CH- OHz-CH: CH2 CHrC A reaction product of dicyclohexylamine and a polyvinyl methane sulfonate was prepared as follows:

Ten grams of polyvinyl methane sulfonate was mixed With 100 cc. of dioxane, 100 g. of dicyclohexylamine, and'5 cc. of water. This mixture was heated on a steam bath for 72 hours, and then poured into water. A light yellow resin separated. This resin was washed in water and dried. It was soluble in dilute acid, and could be reprecipitated by adding alkali to the acid solution.

It is believed to contain the following basic unit:

OKs-CH2 /'CH2'-CH2 CE: CH2 CH2-CH2 3. Polymers or copolymers of compounds having a, combined dialkylamine acrylic group, and containing the basic unit COX N x z where R1 and R2 are CH3, CH3(CH2)n and X is OH, NHz, alkoxy, or alkyl 4. Polymers or copolymers of compounds containing a vinyl ester group in which the acyl group is derived from an N-dialkylamino acid,

and containing the basic unit ...oH,-oH R,

O-(|.|7CH2N where R1 and R2 are CH3, CHa(CHa)n and 5. Polyvinyl acetals derived from an alcohol containing a dialkylamino group. These compounds may be prepared according to th method disclosed in Swan U. S. Patent 2,358,836, granted September 26, 1944.

The above types :of compounds may be used" as the tertiary amines or may be converted into corresponding quaternary ammonium compounds to increase their effectiveness. Quaternary ammonium compounds are strongly ionized at any value of pH. However, ternary nitrogen compounds are strong enough bases 50 that there is considerabl ionization at a pH of the order of 3'zto 4, which is commonly used in the relief imbibition process for transfer of dyes from gelatin matrices. Quaternization may be carried out by reacting th tertiary compound, before .or after polymerization, with an ester, such as methyl p-toluenesulfonate. Alkyl sulfates, .alkyl halides or'other esters may be used.

By copolymer we mean to include those resins Example 8 A film was coated with a mixture of 40 grams of gelatin and 2 grams of the product of Example 2 at pH 4.5. This film was used for transfer of an acid dye, Aliza-rim Saphirol B, C. I. 1054 from a matrix of hardened gelatin. The compound acted as a mordant, improving the definition of the image over that of a corresponding image transferred to a film coated with gelatin hardened with chrome alum.

Example 9 Poly-c-diethylaminoethyl methacrylate acetate (A) and its quaternary salt (B) were separately mixed with the dye [(3-ethyl2(3) benzoxazylidene)ethylidene] l p sulfophenyl- 3-methyl-5-pyrazo1one in the proportions indicated in the following table and were coated on glass plates. No bleeding of dye was indicated when the coatings were immersed in distilled water. The coatings were overcoated with a fast unsensitized gelatino silver halide emulsion and tested photographical'ly by exposing and developing the photographic layer. The resultsshown in the following table indicate that difiusion of the dye into the emulsion was stopped both by the poly-,s-diethylamino ethyl methac-rylate and its quaternary salt since there was :no loss of. speed corresponding to that in the undercoat of gelatin containing the dye only.

Undcrcoat Speed 7 Plain gelatin G30 1. 38 0.14 g. dye in cc. 5% gelatin 330 0.61 0.14 g. dye 0.17 g. (A) in 100 cc. 5% gelatin 955 0.84 0.14 g. dye 0.35 g. (B) in 100 0c. 5% gelatin 590 1.07

acrylate type, wherein the alpha carbon atom contains two different substituents, one of which is a dialkylamine group, and the other is a substituent other than hydrogen. These polymers may be homopolymers or they may (be copolymers. The dialkylamino compound may be a tertiary amine or it may be quaternized depend ing upon conditions of use.

What we now claim and desire to secure by U. S. Letters Patent is:

l. A photographic element comprising a support having thereon at least two gelatin layers, at least one of said gelatin layers being a silver halide emulsion layer and at least one of said gelatin layers having distributed therein a substantially water-insoluble salt of a water-soluble acid dye with a polymeric mordant comprising a linear polymer of a monoethylenically unsaturated polymerizable compound having periodically occurring dialkylamino groups attached thereto.

2. A photographic element comprising a support having thereon at least two gelatin layers, at least one or" said gelatin layers being a silver halide emulsion layer and at least one of said gelatin layers having distributed therein a substantially water-insoluble salt of a water-soluble acid dye with a polyvinyl polymer having recurring groups attached to said polymer, where R1 and R2 are selected from the group consisting of alkyl groups, alicyolic groups and structures in which R1 is -CH2X and R2 is CH2Y, X and Y together representing the atoms necessary to complete a saturated heterocyclic ring.

3. A light-sensitive photographic element comprising a support having thereon at least two gelatin layers, at least one of said gelatin layers being a silver halide emulsion layer, and at least one of said gelatin layers having distributed therein a polymeric mordant adapted to fix a soluble acid dye in said gelatin, said mordant being a poly fl-N-dialkyl amino carboxylic acid vinyl ester.

4. A light-sensitive photographic element comprising a support having thereon at least two gelatin layers, at least one of said gelatin layers being a silver halide emulsion layer, and at least one of said gelatin layers having distributed therein a polymeric mordant adapted to fix a.

soluble acid dye in said gelatin, said mordant being a quaternary ammonium salt of a poly p-N- dialkyl amino carboxylic acid vinyl ester.

5. A light-sensitive photographic element comprising a support having thereon at least two gelatin layers, at least one of said gelatin layers being a silver halide emulsion layer, and at least one of said gelatin layers having distributed therein a polymeric mordant adapted to fix a soluble acid dye in said gelatin, said mordant being a poly dialkylamino carboxylic acid vinyl amide.

8 6. A light-sensitive photographic element comprising a support having thereon at least two gelatin layers, at least one of said gelatin layers being a silver halide emulsion layer, and at least one of said gelatin layers having distributed therein a polymeric mordant adapted to fix a 501- uble acid dye in said gelatin, said mordant being a 8-diethylaminoethyl-methacrylate polymer.

7.. A light-sensitive photographic element comprising a support having thereon at least two gelatin layers, at least one of said gelatin layers being a silver halide emulsion layer, and at least one of said gelatin layers having distributed therein a polymeric mordant adapted to fix a soluble acid dye in said gelatin, said mordant being polymeric s-diethylaminoethyl-methacrylate metho-methylsulfate.

8. A light-sensitive photographic element comprising a support having thereon at least two gelatin layers, at least one of said gelatin layers being a silver halide emulsion layer, and at least one of said gelatin layers having distributed therein a polymeric mordant adapted to fix a soluble acid dye in said gelatin, said mordant being an N-vinyl dialkylamine polymer.

v9. 7 A light-sensitive photographic element comprising a support having thereon at least two gelatin layers, at least one of said gelatin layers being a silver halide emulsion layer, and at least she of said gelatin layers having distributed therein a polymeric mordant adapted to fix a 501- uble acid dye in said gelatin, said mordant being a reaction product of diethyl-amine and a vinyl' benzene sulfonate-vinyl alcohol copolymer.

10. A photographic element comprising a support having thereon at least two gelatin layers, at least one of said gelatin layers being a silver halide emulsion layer and at least one of said gelatin layers having distributed therein a substantially water-insoluble salt of a water-soluble acid dye with a polymeric mordant comprising a B- diethylaminoethyl-methacrylate polymer.

11. A photographic element comprising a support having thereon at least two gelatin layers, at least one of said gelatin layers being a silver halide emulsion layer and at .least one of said gelatin layers having distributed therein a substantially water-insoluble salt of a water-soluble acid dye with a polymeric mordant comprising polymeric, p diethylaminoethyl methacrylate metho methylsulfate.

References Citedin the file'of this patent UNITED STATES PATENTS 

1. A PHOTOGRAPHIC ELEMENT COMPRISING A SUPPORT HAVING THEREON AT LEAST TWO GELATIN LAYERS, AT LEAST ONE OF SAID GELATIN LAYERS BEING A SILVER HALIDE EMULSION LAYER AND AT LEAST ONE OF SAID GELATIN LAYERS HAVING DISTRIBUTED THEREIN A SUBSTANTIALLY WATER-INSOLUBLE SALT OF A WATER-SOLUBLE ACID DYE WITH A POLYMERIC MORDANT COMPRISING A LINEAR POLYMER OF A MONOETHYLENICALLY UNSATURATED POLYMERIZABLE COMPOUND HAVING PERIODICALLY OCCURRING DIALKYLAMINO GROUPS ATTACHED THERETO. 